Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems
The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBut) of [Ru(NCCH2CN)(PPh3)2Cp]PF6 (1) gives Ru{N=C=CH(CN)}(PPh3)2Cp (2), which adds a second [Ru(PPh3)2Cp]+ unit to give [{Ru(PPh3)2Cp}2(μ-NCCHCN)]+ (3). Attempted deprotonation of the latter t...
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| Format: | Journal Article |
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Elsevier
2004
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| Online Access: | http://hdl.handle.net/20.500.11937/29715 |
| _version_ | 1848752879105474560 |
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| author | Bruce, M. Buntine, Mark Costuas, K. Ellis, B. Halet, J. Low, P. Skelton, B. White, A. |
| author_facet | Bruce, M. Buntine, Mark Costuas, K. Ellis, B. Halet, J. Low, P. Skelton, B. White, A. |
| author_sort | Bruce, M. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBut) of [Ru(NCCH2CN)(PPh3)2Cp]PF6 (1) gives Ru{N=C=CH(CN)}(PPh3)2Cp (2), which adds a second [Ru(PPh3)2Cp]+ unit to give [{Ru(PPh3)2Cp}2(μ-NCCHCN)]+ (3). Attempted deprotonation of the latter to give the μ-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{N=C=C(CN)2}(PPh3)2Cp (4) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)CN}]PF6 (5), and with pentacyanopropenide, Ru{N=C=C(CN)C(CN)C(CN)2}(PPh3)2Cp (6) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)C(CN)C(CN)CN}]PF6 (7). The Ru(dppe)Cp* analogues of 6 and 7 (8 and 9) were also prepared. Thermolysis of 6 (refluxing toluene, 12 h) results in loss of PPh3 and formation of the binuclear cyclic complex {Ru(PPh3)Cp[μ-N=C={C(CN)=C(CN)2}CN]}2 (10). The solid-state structures of 2–4 and 8–10 have been determined and the nature of the isomers shown to be present in solutions of the binuclear cations 7 and 9 by NMR studies has been probed using Hartree–Fock and density functional theory. |
| first_indexed | 2025-11-14T08:15:38Z |
| format | Journal Article |
| id | curtin-20.500.11937-29715 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T08:15:38Z |
| publishDate | 2004 |
| publisher | Elsevier |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-297152017-09-13T15:25:59Z Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems Bruce, M. Buntine, Mark Costuas, K. Ellis, B. Halet, J. Low, P. Skelton, B. White, A. DFT Redox properties Electronic interactions Conformations Cyanocarbon Ruthenium The preparation of several ruthenium complexes containing cyanocarbon anions is reported. Deprotonation (KOBut) of [Ru(NCCH2CN)(PPh3)2Cp]PF6 (1) gives Ru{N=C=CH(CN)}(PPh3)2Cp (2), which adds a second [Ru(PPh3)2Cp]+ unit to give [{Ru(PPh3)2Cp}2(μ-NCCHCN)]+ (3). Attempted deprotonation of the latter to give the μ-NCCCN complex was unsuccessful. Similar chemistry with tricyanomethanide anion gives Ru{N=C=C(CN)2}(PPh3)2Cp (4) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)CN}]PF6 (5), and with pentacyanopropenide, Ru{N=C=C(CN)C(CN)C(CN)2}(PPh3)2Cp (6) and [{Ru(PPh3)2Cp}2{μ-NCC(CN)C(CN)C(CN)CN}]PF6 (7). The Ru(dppe)Cp* analogues of 6 and 7 (8 and 9) were also prepared. Thermolysis of 6 (refluxing toluene, 12 h) results in loss of PPh3 and formation of the binuclear cyclic complex {Ru(PPh3)Cp[μ-N=C={C(CN)=C(CN)2}CN]}2 (10). The solid-state structures of 2–4 and 8–10 have been determined and the nature of the isomers shown to be present in solutions of the binuclear cations 7 and 9 by NMR studies has been probed using Hartree–Fock and density functional theory. 2004 Journal Article http://hdl.handle.net/20.500.11937/29715 10.1016/j.jorganchem.2004.07.030 Elsevier restricted |
| spellingShingle | DFT Redox properties Electronic interactions Conformations Cyanocarbon Ruthenium Bruce, M. Buntine, Mark Costuas, K. Ellis, B. Halet, J. Low, P. Skelton, B. White, A. Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
| title | Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
| title_full | Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
| title_fullStr | Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
| title_full_unstemmed | Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
| title_short | Some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
| title_sort | some ruthenium complexes containing cyanocarbon ligands: syntheses, structures and extent of electronic communication in binuclear systems |
| topic | DFT Redox properties Electronic interactions Conformations Cyanocarbon Ruthenium |
| url | http://hdl.handle.net/20.500.11937/29715 |